Phosphoramidates and phosphonamidates

ABSTRACT

This invention discloses new compounds of the formula   p wherein R1 is alkyl; and R2 and R3 are each selected from the group consisting of hydrogen and alkyl; X1, X2, X3 and X4 are independently selected from the group consisting of oxygen and sulfur; m and n are each integers from 0 to 1; Z1 is selected from the group consisting of alkyl, phenyl, alkylphenyl, halophenyl and alkyl-halophenyl; and Z2 is selected from the group consisting of hydrogen and Z1, provided that when Z2 is hydrogen then n is zero. Further disclosed are insecticidal and acaricidal compositions which comprise an inert carrier and a compound of the above description.

United States Patent n91 Stach [111 3,920,772 1*Nov. 18,1975

I [75] Inventor:

[ PHOSPHORAMIDATES AND PHOSPHONAMIDATES Leonard J. Stach, Riverside,Ill.

[73] Assignee: Velsicol Chemical Corporation,

Chicago, Ill.

[ Notice: The portion of the term of this patent subsequent to Nov. 18,1992, has been disclaimed.

[22] Filed: Sept. 5, 1972 21 Appl. No.: 286,488

[52] US. Cl 260/944; 424/211 [51] Int. Cl. C07F 9/24; AOlN 9/36 [58]Field of Search 260/944 [56] References Cited 7 UNITED STATES PATENTS3,574,793 4/1971 Richter et al. 260/944 Primary Examiner-Anton H. SuttoAttorney, Agent, or Firm-Robert J. Schwartz; Dietmar H. Olesch [57]ABSTRACT s This invention discloses new compounds of the formula .phenyland alkyl-halophenyl; and Z is selected from the group consisting ofhydrogen and Z, provided that when Z is hydrogen then n is zero. Furtherdisclosed are insecticidal and acaricidal compositions which comprise aninert carrier and a compound of the above description.

' 5 Claims, No i wings PHOSPHORAMIDATES AND PHOSPHONAMIDATES Thisinvention relates to new compositions of matter and more specificallyrelates to new compounds of the formula I I wherein R is alkyl; R and Rare each selected from ing of hydrogen and Z, provided that when Z ishydrogen then n is zero.

In a preferred embodiment of the present invention R is lower alkyl; Rand R are each selected from the group consisting of hydrogen and loweralkyl; Z is selected from the group consisting of lower alkyl, phenyl,

lower alkylphenyl, chlorophenyl, bromophenyl and lower alkyl-halophenyl;and Z is selected from the group consisting of hydrogen and thepreferred Z provided that when Z is hydrogen then 11 is zero.

The term lower as used herein represents a straight or branched carbonchain of up to ten carbon atoms.

The new compounds of the present invention are unexpectedly useful asinsecticides and acaricides. Thus, a further embodiment of the presentinvention resides in an insecticidal or acaricidal compositioncontaining as the essential active ingredient a compound of the presentinvention. A still further embodiment of this invention is a method ofcontrolling insects or-acarids by applying to the insects or acarids aninsecticidal or acaricidal composition of this invention. I

The newcompounds of the prese'nt invention can be readily prepared byreacting a compound of the formula R R Z (ll) wherein R R, X, X,X, XLZ,2, m and n are as heretofore described with a molar or excess amount of2 H tor halide. The washed product can then be dried to yield a'compoundof this invention.

The compounds of formula II can be prepared from an alkali metalphosphoramidate or'phosphonamidate of the formula wherein M is an alkalimetal and R R X, X X Z and m are as heretofore described by reactionwith a compound of the formula Hal (IV) wherein Hal designates ahalogen, preferrably chlorine or bromine, and 2*, X" and n are asheretofore described. This reaction can be effected by adding thecompound of formula IV or a solution of the compound of formula IV in aninert organic solvent such as methyl ethyl ketone, to a solution of thecompound of formula III in an inert organic solvent. This reactionmixture can be heated'atits reflux temperature, with stirring, for aperiod of from about 4 to about 48 hours. After the reaction iscompleted thereaction mixture can be an alkoxyamine or alkoxyaminehydrochloride. This 1 reaction can be effected by heating the reactantsin an inert organic solvent such as ethanol in the presence of a basesuch as pyridine which liberates the methoxya- 'mine from its salt, fora period of from about kto about 24 hours. The heating can beconveniently carried out at the reflux temperature of the reactionmix-..

.the ether solution with water to remove the acid accephyde,gx-chloropropanal,

filtered to remove the alkali metal halide which has formed. The desiredproduct can be conveniently recovered as a residue upon evaporation ofthe solvents from the remaining solution. The product can then be usedas such or can be further purified by washing, distillation or othercommon methods known in the art. The alkali metal phosphoramidates andphosphonamidates of formula III which are used in the prephyde,2-methyl-4-chlorophenyl chloroacetaldehyde,

4-iodophenyl 4-bromophe'nyl chloroacetaldehyde, chloroacetaldehyde,4-fluorophenyl' chloroacetaldehyde, Z-methyI- I,6-dichlorophenylchloroacetaldehyde, 2,4-diethylphenyl chloroacetaldehyde, 4-propylphenylchloroacetaldehyde, 3-pentylphenyl chloroacetaldehyde, 4-diethylphenylchloroacetaldehyde, me-

- thoxy. chloroacetaldehyde, pentyloxy chloroacetaldehyde,,phenoxychloroacetaldehyde, 2-methyl-4-chlorophenoxy chloroacetaldehyde,3,4-dibromophenylthio chloroacetaldehyde, methylthio chloroacetaldehyde,decylthio chloroacetaldehyde and the like.

The compounds of the present invention can also be prepared by reactinga compound of formula III with an alkoxyimine of the formula After thereaction is completed the reaction mixture.

can be filtered to remove the alkali metal halide which has formed. Thedesired product can be conveniently recovered as a residue uponevaporation of the solvent from the remaining solution. The product canthen be used as such or can be further purified by washing, distillationor chromatography if the product is an oil, or by trituration,recrystallization or other common methods well known in the art if theproduct is a solid.

The alkoxyimine of formula V can be prepared by reacting an aldehyde offormula IV heretofore described, with an alkoxyamine or alkoxyaminehydrochloride. This reaction can be readily effected by combining thereactants in an inert reactionmedium such as water, ethanol or the likeand stirring the mixture at room temperature for a period of up to about4 hours. After this time the desired. product can be recovered byextraction of the oil phase formed if water was employed as the reactionmedium, or upon evaporationof the reaction medium if the product issoluble therein. The recovered product can then be used as such or canbe further purified by conventional means[ The preparation of thecompounds of the present invention is more specifically illustrates inthe following examples.

EXAMPLE 1 Preparation of l-Chloro-2-Methoxyiminoethane EXAMPLE 2Preparation of S-(Z-Methoxyiminoethyl) O-MethylN,N-Dimethylthiolophosphoramidate Potassium O-methylN,N-dimethylthiolophosphoramidate (19.3 grams; 0.1 mole), l-chloro-2-methoxyiminoethane (10.7 grams; 0.1 mole) and methyl ethyl ketone (80ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer and reflux condenser. The reaction mixture is heated at reflux,with stirring, for a period-of about 18 hours. After this time thereaction mixture is cooled to room temperature and is filtered. Thefiltrate is evaporated and the residue dissolvedin ethenThe ethersolution is 4 then washed with water and is dried over anhydrousmagnesium sulfate. The dried solution is stripped of solvent to yieldthe desired product S-(2-methoxyiminoethyl) O-methylN,N-dimethylthiolophosphoramidate.

EXAMPLE 3 Preparation of S-(2-Methoxyimin0ethyl) O-(3,4-dichlorophenyl)N-Isopropylthiolophosphoramidate Potassium O-(3,4-dichlorophenyl)N-isopropylthiolophosphoramidate (31.6 grams; 0.1 mole), l-chloro-2-methoxyiminoethane (10.7 grams; 0.1 mole) and methyl ethyl ketone (100ml) are charged into a glass reaction vessel equipped with a mechanicalstirrer and reflux condenser. The reaction mixture is heated at reflux,with stirring, for a period of about 16 hours. After this'time thereaction mixture is cooled to room temperature and is filtered. Thefiltrate is evaporated and the residue dissolved in ether. The ethersolution is washed with water and is dreied over anhydrous magnesiumsulfate. The dried solution is stripped of solvent v to yield thedesired product S-(2-methoxyiminoethyl) O-(3,4-dichlorophenyl)phoramidate asthe residue.

N-isopropylthiolophos- EXAMPLE 4 Preparation of1-Chloro-1-Phenyl-2-Propoxyiminoethane EXAMPLE 5 Preparation of S-(l-Phenyl-2-Propoxyiminoethyl) Methyl-N,N-DimethylthiolophosphonamidatePotassium methyl-N,N-dimethylthiolophosphonamidate (18 grams; 0.1 mole),l-chloro-l-phenyl-Z- propoxyiminoethane (19.0 grams; 0.1 mole) and Imethyl ethyl ketone ml) are charged into a glass reaction vesselequipped with a mechanical stirrer and reflux condenser. The reactionmixture is heated at reflux, with stirring for a period of about 14hours. After this time the reaction mixture is cooled to roomtemperature and is filtered. The filtrate is evaporated and the residuedissolved in ether. The ether solution is washed with water and is driedover anhydrous magnesium sulfate. The dried solution is stripped ofsolvent to 'desired EXAMPLE 6 Preparation of S-FormylmethylS-(2-Methyl-4-Bromophenyl) N-t-Butyldithiolophosphoramidate A 45 percentaqueous solution of chloroacetaldehyde (7.85 grams; 0.10 mole),potassium S-'( 2-methyl- 4-brornophenyl)N-t-butyldithiolophosphoramidate (39.2 grams; 0.1 mole) and water (30ml) are charged 'into a glass reaction vessel equipped with a mechanicalv stirrer. The reaction mixture is heated slowly, with stir- EXAMPLE 7Preparation of S-(Z-Pentyloxyiminoethyl) S-(2-Methyl-4-Bromophenyl)N-t-Butyldithiolophosphoramidate S-FormylmethylS-(2-methyl-4-bromophenyl) N-tbutyldithiolophosphoramidate (21 grams;0.05 mole), pentyloxyamine hydrochloride (8.37 grams; 0.06 mole),pyridine (4.7 grams; 0.06 mole) and absolute ethanol (40 ml) are chargedinto a glass reaction vessel equipped with a mechanical stirrer andreflux condenser. The reaction mixture is heated at reflux, withstirring, for a period of about 2 hours. After this time the reactionmixture is subjected to distillation to remove the ethanol and unreactedamine. The residue is dissolved in ether and the ether solution iswashed with water. The washed ether solution is then dried overanhydrous magnesium sulfate and filtered. The filtrate is thenevaporated to yield the desired product S-(Z-pentyloxyiminoethyl)S-(2-methyl-4-bromophenyl) N-tbutyldithiolophosphoramidate as theresidue.

Additional compounds within the scope of the present invention can beprepared by the procedure of the foregoing examples. In the followingexamples are given the essential starting materials for preparing theindicated named compounds.

EXAMPLE 8 Potassium O-(4-isopropylphenyl) N,N-dipentylphosphoramidatemethoxy chloroacetaldehyde ethoxyamine O-( l-methoxy-2-ethoxyiminoethyl)O-(4-isopropylphenyl) N,N-dipentylphosphoramidate.

EXAMPLE 9 Potassium O-(3,4-dibromophenyl) N-decylphosphoramidatemethylthio chloroacetaldehyde methoxyamine hydrochlorideO-(l-methylthio-2- methoxyiminoethyl) O-(3,4-dibromophenyl) N-decyl-'phosphoramidate.

EXAMPLE 10 Potassium S-(2-pentyl-4-iodophenyl)N,N-diethylthiolothionophosphoramidate 2-methylphenyl chloroacetaldehydedecyloxyamine O-[l-(Z-methylphenyl)-2-decyloxyiminoethyl]S-(2-pentyl-4-iodophenyl) N,N-diethylthiolothionophosphoramidate.

EXAMPLE 1 1 Potassium phenyl-N,N-dimethylthiolophosphonamidate4-chlorophenyl chloroacetaldehyde methoxyamine hydrochlorideS-[1-(4-chlorophenyl)-2- methoxyiminoethyl]phenyl-N,N-dimethylthiolophosphonamidate.

EXAMPLE 12 Potassium O-(4-pentylphenyl) N-isopropylthiolophosphoramidate3-iodophenyl chloroacetaldehyde, butoxyamine S-[l-(3-iodophenyl)-2-butoxyiminoethyl] O-(4-pentylphenyl)N-isopropylthiolophosphoramidate.

EXAMPLE l3 Potassium O-(4-fluorophenyl)N,N-dimethylthionophosphoramidate 3-propyl-5-bromophenoxychloroacetaldehyde methoxyamine hydrochloride O- l-(3-propyl-5-bromophenoxy)- 2-methoxyiminoethyl] O-(4-fluorophenyl)N,N-dimethylthionophosphoramidate.

EXAMPLE 14 Potassium S-(2-decyl-4-chlorophenyl)N,N-dimethyldithiolothionophosphoramidate +a-chlorodecanal butoxyamineS-( l-octyl-2-methoxyiminoethyl) S- (2-decyl-4-chlorophenyl)N,N-dimethyldithiolothionophosphoramidate.

Additional compounds within the scope of the present invention which canbe prepared by the procedures of the foregoing examples areS-(2-methoxyiminoethyl) O-ethyl N -t-butylthiolophosphoramidate,S-(lethyl-2-methoxyiminoethyl)isopropyl-N,N-dimethylthiolophosphonamidate, S-(l-decyl-Lmethoxyiminoethyl) hexyl-N,N-diethylthiolophosphonamidate, S-(l butoxy-Z-methoxyiminoethyl) -O-decylN-isopropylthiolothionophosphoramidate, S-(l-pentylthio-Z-ethoxyiminoethyl) O-(2,4-dimethylphenyl)N-t-butylthiolophosphoramidate, O-(2-methoxyiminoethyl) O-ethylN-isopropylphosphoramidate, S-(2-methoxyiminoethyl) S-ethylN-isopropyldithiolophosphoramidate, S-(2-methoxyiminoethyl) S-ethylN-isopropyldithiolothionophosphoramidate, S-(2-methoxyiminoethyl)O-ethyl N-t-butylthiolophosphoramidate and the like.

For practical use as insecticides or acaricides, the compounds of thisinvention are generally incorporated into insecticidal or acaricidalcompositions which comprise an inert carrier and an insecticidally oracaricidally toxic amount of such a compound. Such insecticidal oracaricidal compositions, which can also be called formulations, enablethe active compound to be applied conveniently to the site of the insector acarid infestation in any desired quantity. These compositions can besolids such as dusts, granules or Wettable powders; or they can beliquids such as solutions, aerosols or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,pyrophyllite, and the like. Granular formulations can be preparedbyjmpregnating the compound, usually dissolved in a suitablesolvent,onto and into granulated carriers such as the attapulgites orthe vermiculites, usually of a particle size range of from about 0.3 to1.5 mm. Wettable powders, which can be dispersed in water and/or oil toany desired concentration of the active compound can be 7 prepared byincorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofinsecticides or acaricides can be dispersed under superatmosphericpressure as aerosols. However, preferred liquid insecticidal oracaricidal compositions are emulsifiable concentrates, which comprise anactive compound according to this invention and as the inert carrier, asolvent and an emulsifier. Such emulsifiable concentrates can beextended with water and/or oil to any desired concentration of activecompound for application as sprays to the site of the insect or acaridinfestation. The emulsifiers most commonly used in these concentratesare nonionic or mixtures of nonionic with anionic surfaceactive agents.I

A typical insecticidal or acaricidal composition according to thisinvention is illustrated by the following example, in which thequantities are in parts by weight.

EXAMPLE 15 Preparation of a Dust The above ingredients are mixed in amechanical grinder-blender and are ground until a homogeneous,free-flowing dust of the desired particle size is obtained. This dust issuitable for direct application to the site of the insect or acaridinfestation.

The compounds of this invention can be applied as insecticides oracaricides in any manner recognized by the art. One method fordestroying insects or acarids comprises applying to the locus of theinsect or acarid infestation, an insecticidal or acaricidal compositioncomprising an inert carrier and, as an essential active ingredient, in aquantity which is toxic to said insects or acarids, a compound of thepresent invention. The concentration of the new compounds of thisinvention in the insecticidal or acaricidal compositions will varygreatly with the type of formulation and the purpose for which it isdesigned, but generally the insecticidal or acaricidal compositions willcomprise from about 0.05 to about 95 percent by weight of the activecompounds of this invention. In a preferred embodiment of thisinvention, the insecticidal or acaricidal compositions will comprisefrom about to 75 percent by weight of the active compound. Thecompositions can also comprise such additional substances as otherpesticides, stabilizers, apreaders, deactivators, adhesives, stickers,fertilizers, activators, synergists and the like.

The compounds of the present invention are also useful when combinedwith other insecticides or acaricides in the compositions heretoforedescribed. These other insecticides or acaricides can comprise fromabout 5% to about 95% of the active ingredients in the compositions. Useof the combinations of these other insecticides or acaricides with thecompounds of the present invention provide insecticidal and/oracaricidal compositions which are more effective in controlling insectsor acarids and often provide results unattainable with separatecompositions of the individual compounds. The other insecticides oracaricides with which the compounds of this invention can be used in theinsecticidal or acaricidal compositions to control insects or acaridsinclude halogenated compounds such as DDT, methoxychlor, TDE, lindane,chlordane, isobenzan, aldrin, dieldrin, heptachlor, endrin, mirex,endosulfon, dicofol and like; organic phosphorus compounds such as TEPP,schradan, ethion, parathion, methyl parathion, EPN, demeton,carbophenothion, phorate, zinophos, diazinon, malathion, mevinphos,dimethoate, DBD, ronnel, oxydemeton-methyl, dicapthon, chlorothion,phosphamidon, naled, fenthion, trichlorofon, DDVP and the like; organicnitrogen compounds such as dinitro-o-cresol, dinitrocyclohexylphenol,DNB, DNP, binapacril, azobenzene, and the like; organic carbamatecompounds such as carbaryl, ortho 5353 and the like; organic sulfurcompounds such as phenothiazine, phenoxathin, lauryl thiocyanate,[bis(2-thiocyanoethyl)ether], isobornyl thiocyanoacetate and the like;as well as such substances usually referred to as fumigants, as hydrogencyanide, carbon tetrachloride, calcium cyanide, carbon disulfide,ethylene dichloride, propylene dichloride, ethylene dibromide, ethyleneoxide, methyl bromide, paradichlorobenzene and the like.

The compounds of the present invention can also be combined withfungicidal and nematocidal chemical compounds to form pesticidalcompositions useful for the control of fungi and in some cases soilnematodes as well as insects or acarids. Typical examples of suchfungicidal chemical compounds are ferbam, nabam, zineb, ziram, thiram,chloranil, dichlone, glyodin, cycloheximide, dinocap, maneb, captan,dodine, PCNB, p-dimethylaminobenzene diazo sodium sulfonate and thelike; while examples of nematocidal compounds are chloropicrin,0,0-diethyl O-(2,4-dichlorophenyl) phosphorothioate,tetrachlorothiophene, dazomet, dibromochloropropane and the like.

The new compounds of this invention can be used in many ways for thecontrol of insects or acarids. Insecticides or acaricides which are tobe used as stomach poisons or protective materials can be applied to thesurface on which the insects or acarids feed or travel. Insecticides oracaricides which are to be used as contact poisons or eradicants can beapplied directly to the body of the insect or acarid, as a residualtreatment to the surface on which the insect or acarid may walk orcrawl, or as a fumigant treatment of the air which the insect or acaridbreathes. In some cases, the compounds applied to the soil or plantsurfaces are taken up by the plant, and the insect or acarids arepoisoned systemically.

The above methods of using insecticides are based on the fact thatalmost all the injury done by insects is a direct or indirect result oftheir attempts to secure food. Indeed, the large number of destructiveinsects can be classified broadly on the basis of their feeding habits.Among the insects which can be effectively controlled by the compoundsof the present invention are the chewing insects such as the Mexicanbean beetle and the southern armyworm; the piercing-sucking insects,such as the pea aphid, the cereal leaf beetle, the housefly, the grapeleafhopper, the chinch bug, the lygus bug, the oyster shell scale, theCalifornia red scale, the Florida red scale, the soft scale andmosquitoes; the internal feeders, including borers, such as the Europeancorn borer, the peach twig borer and the corn earworm, worms or weevils,such as the codling moth, the alfalfa weevil, the cotton boll weevil,the pink boll worm, the plum curculio,the red banded leaf roller, themelonworm, the cabbage looper and the apple maggot, leaf miners, such asthe apple leaf miner, the birch leaf miner and the beet leaf miner, andgall insects such as the wheat joint worm and the grape phylloxera.lnsects which attack below the surface of the ground are classified assubterranean insects and include such destructive pests as the woolyapple aphid, the Japanese beetle, the onion maggot and the cornrootworm.

Mites and ticks are not true insects. Many economically importantspecies of mites and ticks can be controlled by the compounds of thepresent invention such as the red spider mite, the two-spotted mite, thestrawberry spider mite, the citrus rust mite, the cattle tick, thepoultry mite, the citrus red mite and the European red mite. Chemicalsuseful for the control of mites are often called miticides, while thoseuseful for the control of both mites and ticks are known specificallyasacaricities.

The quantity of active compound of this invention to be used for insector acarid control will depend on a variety of factors, such as thespecific insect involved, intensity of the infestation, weather, type ofenvironment, type of formulation, and the like. For example, theapplication of only one or two ounces of active chemical per acre may beadequate for control of a light infestation of an insect or acarid underconditions unfavorable for its feeding, while a pound or more of activecompound per acre may be required for the control of a heavy infestationof insects or acarids under conditions favorable to their development.

The insecticidal activity of the compounds of the present invention canbe demonstrated by experiments carried out for the control of a varietyof insects.

in one experiment, designated as the housefly knockdown test, fiftythree day old unsexed adult houseflies (Musca Domestica) areanesthetized with carbon dioxide gas and placed into a fine mesh cage.The flies'are allowed to recover completely from the effects of thecarbon dioxide gas and are then sprayed with a formulation containingthe indicated concentration of test compound. After 30 minutes theknockdown value of the test compound is determined. Knockdown isconsidered as an individual fly that is unable to move its body length,and the knockdown value is the percent of down flies based upon thenumber of down flies in comparison to a control.

The insecticidal activity of the compounds of this invention can furtherbe illustrated in experiments carried out for the control of the peaaphid (Acyrthasiphon pisum) by contact. In these experiments ten day oldLaxton pea plants contained in small plastic pots are each infested withten adult pea aphids. The plants and pea aphids are then sprayed withthe test compound formulated as an aqueous emulsion of an acetonesolution can be demonstrated in experiments for thesystemic control ofpea aphids. In these experiments day old Laxton pea plants which havepreviously been watered with 30 ml of water containing the test compoundat the indicated concentration, are infested with ten, newly molted,adult pea aphids. The infested plants are then placed in a holdingchamber at 65F. for a period of 48 hours where they are supplied withwater and light as required. After this time the mortality of the peaaphids is determined and rated on a percent basis in comparison to anuntreated control.

The acaricidal activity of the compounds of the present invention can bedemonstrated in experiments carried out for the control of thetwo-spotted spider mite (Tetranychus urticae).

in one experiment wherein the activity of the compounds of the presentinvention as contact poisons is determined, the test compounds areformulated at the desired dosages, as aqueous emulsions of acetonesolutions and are sprayed onto Henderson bush lima bean plants, eachinfested with about adult two-spotted spider mites. The treated plantsare then placed into a holding room and were supplied with their dailyrequirement of water and light. After a period of 5 days the mortalityof the mites is determined and, is rated on a percentage basis incomparison to untreated controls.

In another experiment, the systemic activity of the compounds of thepresent invention, for the control of v the two-spotted spider mite canbe demonstrated. In this experiment, 5 day old Henderson bush lima beanplants are each watered .with 30 ml of a formulation mites is determinedand rated on a percent basis in comparison to untreated controls.

I claim: '1. A compound of the formula wherein R is lower alkyl; R and Rare each selected from the group consisting of hydrogen and lower alkyl;X X*-, X and X are independently selected from the group consisting ofoxygen and sulfur; m is an integer from 0 to l, n is zero; Z is selectedfrom the group consisting of lower alkyl, phenyl, lower alkylphenyl,halophenyl and lower alkyl-halophenyl; and Z is hydrogen.

2. The compound of claim 1, S-(Z-methoxyiminoethyl) O-methylN,N-dimethylthiolophosphoramidate..

3. The compound of claim 1, S-(2-methoxyiminoethyl)O-(3,4-dichlorophenyl) N-isopropylthiolophosphoramidate.

4. The compound of claim 1, O-(Z-methoxyiminoethyl) O-ethylN-isopropylphosphoramidate.

5. The compound of claim 1, S-(2-methoxyiminodate.

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1,S-(2-methoxyiminoethyl) O-methyl N, N-dimethylthiolophosphoramidate. 3.The compound of claim 1, S-(2-methoxyiminoethyl) O-(3,4-dichlorophenyl)N-isopropylthiolophosphoramidate.
 4. The compound of claim 1,O-(2-methoxyiminoethyl) O-ethyl N-isopropylphosphoramidate.
 5. Thecompound of claim 1, S-(2-methoxyiminoethyl) O-ethylN-isopropylthiolothionophosphoramidate.